3D Printing ZTA Ceramic-Based Aluminum Borate Whiskers Composite Materials, Preparation Methods, and Applications

Abstract

This invention belongs to the field of ceramic materials technology, specifically relating to 3D printed ZTA ceramic-based aluminum borate whisker composite materials, their preparation methods, and applications. The invention includes the following steps: (1) ball milling and mixing ZTA powder, photosensitive resin, and dispersant to obtain a printing slurry; (2) performing DLP 3D printing on the printing slurry to obtain a ZTA ceramic green body; (3) sintering the ZTA ceramic green body to obtain a ZTA ceramic matrix; (4) immersing the ZTA ceramic matrix in a boric acid solution, followed by ultrasonic soaking, drying, and heat treatment to obtain the 3D printed ZTA ceramic-based aluminum borate whisker composite material. The composite material uses ZTA ceramic as the matrix, which is resistant to high pressure and not easily damaged. By growing aluminum borate whiskers in situ within the matrix channels, a stable bond is formed between the whiskers and the matrix. Efficient oil-water separation is achieved by optimizing the channels and constructing a hydrophilic-oleophobic interface with the whiskers.

Description

Technical Field

[0001] This invention belongs to the field of ceramic materials technology, specifically relating to 3D printed ZTA ceramic-based aluminum borate whisker composite materials, their preparation methods, and applications. Background Technology

[0002] Oily wastewater is one of the main types of industrial and domestic wastewater. Direct discharge without effective treatment will damage aquatic ecosystems and affect water resource recycling. Existing oil-water separation materials have significant drawbacks: ordinary alumina ceramics have low mechanical strength (fracture toughness 3-4 MPa·m). 1 / 2 Under high-pressure separation conditions, the membrane is easily damaged, and its pore structure is disordered, making it easy to be blocked by the oil phase, resulting in flux reduction. The polymer membrane has poor temperature and corrosion resistance, and the oil phase is easy to adhere to the membrane surface, causing "contamination failure". The metal mesh has insufficient hydrophilicity, low separation efficiency (usually ≤98%), and is easily corroded by salt water.

[0003] While there are reports on 3D printing porous ceramics, these technologies do not optimize the pore structure (such as gradient pore size design) and surface interface properties for oil-water separation requirements. There is also research on aluminum borate whisker-modified materials, but such studies often use coating methods to achieve whisker loading, leading to whisker detachment and uneven distribution, failing to form a stable hydrophilic-oleophobic interface. In contrast, ZTA ceramics (zirconia-toughened alumina) exhibit fracture toughness of 5-12 MPa·m. 1 / 2 While it possesses the advantage of high strength, its application in the field of oil-water separation, especially the related technologies for constructing functional interfaces by combining it with in-situ generated aluminum borate whiskers, still needs further development. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a 3D-printed ZTA ceramic-based aluminum borate whisker composite material, which uses ZTA ceramic as the matrix, is resistant to high pressure and not easily damaged; by growing aluminum borate whiskers in situ within the matrix channels, a stable bond is formed between the whiskers and the matrix, and efficient oil-water separation is achieved by relying on the optimized channels and the hydrophilic-oleophobic interface constructed by the whiskers.

[0005] Another objective of this invention is to provide a method for preparing and applying 3D-printed ZTA ceramic-based aluminum borate whisker composite materials.

[0006] The technical solution adopted in this invention is as follows:

[0007] The method for preparing the 3D printed ZTA ceramic-based aluminum borate whisker composite material includes the following steps:

[0008] (1) Add ZTA powder, photosensitive resin and dispersant to a planetary ball mill for ball milling and mixing to obtain printing paste;

[0009] (2) Construct a three-dimensional model using SolidWorks; import the three-dimensional model into a DLP 3D printer for two-dimensional slicing, and use the printing paste obtained in step (1) to print layer by layer to obtain a ZTA ceramic green body with a preset "pore structure";

[0010] (3) The ZTA ceramic green body is placed in a box-type resistance furnace for sintering treatment to obtain the ZTA ceramic matrix;

[0011] (4) The ZTA ceramic matrix was immersed in boric acid solution and ultrasonically soaked at room temperature; then dried and then heat-treated in a muffle furnace to promote the in-situ growth of aluminum borate whiskers in the matrix channels, and finally obtained 3D printed ZTA ceramic matrix aluminum borate whisker composite material.

[0012] The ZTA powder is a composite powder of 3 mol% yttrium oxide-stabilized zirconium oxide and alumina; wherein zirconium oxide accounts for 10-20 wt.% of the total ZTA powder; and the particle size of the ZTA powder is 0.5-2 μm.

[0013] The ZTA powder needs to be dried at 90-110℃ for 9-11 hours before use. This drying process removes the adsorbed moisture from the powder to prevent the agglomeration of the printing paste during subsequent preparation.

[0014] The mass ratio of ZTA powder to photosensitive resin is (80-90):(20-10); the amount of dispersant added is 1-5 wt.% of ZTA powder; and the viscosity of the printing paste is 500-1500 mPa·s.

[0015] The photosensitive resin is composed of KH570, an active diluent, and a photoinitiator in a mass ratio of (70-80):(30-20):3; the active diluent is one or more of 1,6-hexanediol diacrylate, 1,4-hexanediol diacrylate, tripropylene glycol diacrylate, hydroxyethyl acrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, or pentaerythritol acrylate; the photoinitiator is one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, or 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone.

[0016] The dispersant is one of PEG-200, trisodium citrate, or polyacrylic acid.

[0017] In step (2), the model parameters are set through parametric controls, specifically: the model length, width, and height are set to 10mm, 10mm, and 6mm respectively, the surface smoothness parameter is 10, the pore size adjustment parameter is 0.2, the cell type is selected as Gyroid, the period parameter is set to 3-4, the TPMS thickness parameter is 0.5, and the wall thickness is 2mm. Based on the above parameters, a three-dimensional model with corresponding geometric features and pore structure is generated.

[0018] Set the printing layer thickness to 25-40μm and the exposure time to 3-6s.

[0019] In step (3), the sintering process is as follows: the temperature is raised to 600-800℃ at a heating rate of 1-3℃ / min, held for 2-3 hours, then raised to 1550-1650℃ at a heating rate of 4-6℃ / min, held for 2-4 hours, and finally cooled to room temperature at a rate of 3-5℃ / min.

[0020] In step (4), the ultrasonic power is 300-400W and the ultrasonic time is 3-4h.

[0021] In step (4), the boric acid solution consists of deionized water, B2O3, and MoO3. Based on the total mass of the boric acid solution, the mass fraction of B2O3 is 15-25%, the mass fraction of MoO3 is 0.5-1%, and the remainder is deionized water. The B2O3 and MoO3 powders are weighed and added to the deionized water, and then magnetically stirred for 4-6 hours. The heat treatment process is as follows: the temperature is raised to 800-1000℃ at a rate of 5-8℃ / min, and held at that temperature in air for 2-6 hours.

[0022] In step (4), after the ZTA ceramic matrix is ​​ultrasonically soaked in boric acid solution, it is pre-dried at 60-70℃ for 1-1.5h to avoid the residual solution in the pores causing whisker agglomeration.

[0023] The 3D printed ZTA ceramic-based aluminum borate whisker composite material is prepared using the above-mentioned method for preparing 3D printed ZTA ceramic-based aluminum borate whisker composite material. Its water contact angle is ≤25° and oil contact angle is ≥140°, making it suitable for oil-water emulsion separation.

[0024] The aforementioned 3D-printed ZTA ceramic-based aluminum borate whisker composite material is used for oil-water separation of oily wastewater.

[0025] The oily wastewater includes oily wastewater from machining, petrochemicals, and catering, etc. When applied, it is presented as a filter column or ceramic membrane module, with the treatment flow rate controlled at 100-200 L / (m³). 2 Operating pressure: 0.15-0.25 MPa; operating temperature: 20-30℃.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] (1) The present invention uses ZTA ceramic as the matrix, which has a fracture toughness that is more than 40% higher than that of traditional ordinary alumina ceramic. It can effectively withstand the high pressure separation conditions in the water treatment process, fundamentally solving the technical defects of traditional alumina ceramic that is easy to break, and ensuring the structural stability of the material in long-term use.

[0028] (2) This invention uses an in-situ growth process to generate aluminum borate whiskers within the pores of a ZTA ceramic matrix. Stable chemical bonds can be formed between the whiskers and the matrix, avoiding the problems of easy whisker detachment and uneven distribution caused by traditional coating methods. Testing showed that the composite material prepared using this method, when used for oil-water separation of oily wastewater, exhibited excellent cycle stability after 50 cycles, with a separation efficiency decrease of ≤3% and a permeation flux decrease of ≤8%.

[0029] (3) This invention optimizes the pore structure of the ZTA ceramic matrix and constructs a functional interface through in-situ growth of aluminum borate whiskers, enabling the composite material to possess excellent "hydrophilic-oleophobic" properties. In practical applications, under conditions of a flow rate of 100-200 L / (m²·h), an operating pressure of 0.15-0.25 MPa, and a temperature of 20-30℃, the separation efficiency for oily wastewater from machining, petrochemical, and catering industries is ≥99.5%, and the permeation flux is ≥150 L / (m²·h). 2 ·h), which can efficiently meet the needs of oil-water emulsion separation, and solves the pain points of low separation efficiency and rapid flux decay of traditional materials. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the surface structure of the three-dimensional model in step (2) of Example 1;

[0031] Figure 2 This is a schematic diagram of the three-dimensional structure of the three-dimensional model in step (2) of Example 1;

[0032] Figure 3 The image is a scanning electron microscope (SEM) image (×2000) of the 3D printed ZTA ceramic-based aluminum borate whisker composite material prepared in Example 1.

[0033] Figure 4 The image shows a scanning electron microscope (SEM) image (×10000) of the 3D printed ZTA ceramic-based aluminum borate whisker composite material prepared in Example 1. Detailed Implementation

[0034] The present invention will be further described below with reference to the embodiments, but these embodiments do not limit the implementation of the present invention.

[0035] Unless otherwise specified, the raw materials used in the examples and comparative examples are all commercially available materials, and the process methods used in the examples and comparative examples are all conventional methods in the art.

[0036] The following is a description of some of the raw materials used in the examples and comparative examples:

[0037] ZTA powder is a composite powder of 3 mol% yttrium oxide-stabilized zirconium oxide and alumina; of which zirconium oxide accounts for 15 wt.% of the total ZTA powder; the particle size of ZTA powder is 1 ± 0.5 μm; purchased from Beasley New Materials (Suzhou) Co., Ltd.

[0038] Example 1

[0039] The method for preparing the 3D printed ZTA ceramic-based aluminum borate whisker composite material includes the following steps:

[0040] (1) Dry ZTA powder at 100℃ for 10h, add the dried ZTA powder, photosensitive resin and PEG-200 into a planetary ball mill, use zirconium oxide grinding balls, ball-to-material ratio of 4:1, and ball mill and mix at 200r / min for 12h to obtain printing paste;

[0041] The mass ratio of ZTA powder to photosensitive resin is 88:12; the amount of PEG-200 added is 4 wt.% of ZTA powder; the viscosity of the printing paste is 1000 mPa·s; the photosensitive resin is composed of KH570, 1,6-hexanediol diacrylate and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of 75:25:3.

[0042] (2) Construct a three-dimensional model using SolidWorks; import the three-dimensional model into a DLP 3D printer for two-dimensional slicing, and use the printing paste obtained in step (1) to print layer by layer to obtain a ZTA ceramic green body with a preset "pore structure";

[0043] The model parameters are set using parametric controls, specifically: the model length, width, and height are set to 10mm, 10mm, and 6mm respectively; the surface smoothness parameter is set to 10; the pore size adjustment parameter is set to 0.2; the cell type is selected as Gyroid; the period parameter is set to 3.5; the TPMS thickness parameter is set to 0.5; and the wall thickness is set to 2mm. Based on the above parameters, a three-dimensional model with corresponding geometric features and pore structure is generated.

[0044] Set the printing layer thickness to 30μm and the exposure time to 5s;

[0045] (3) The ZTA ceramic green body was placed in a box-type resistance furnace for sintering. The sintering process was as follows: the temperature was raised to 800℃ at a heating rate of 2℃ / min and held for 2h, then raised to 1600℃ at a heating rate of 4℃ / min and held for 2h, and finally cooled to room temperature at a rate of 3℃ / min to obtain the ZTA ceramic matrix.

[0046] (4) The ZTA ceramic matrix was immersed in boric acid solution and ultrasonically soaked for 3.5 h at room temperature and 350 W. After ultrasonic soaking, it was pre-dried at 70 °C for 1 h. Then it was placed in a muffle furnace for heat treatment. The heat treatment process was as follows: the temperature was raised to 900 °C at a rate of 6 °C / min and kept at the temperature in air for 5 h. Finally, the 3D printed ZTA ceramic matrix aluminum borate whisker composite material was obtained.

[0047] The boric acid solution is composed of deionized water, B2O3 and MoO3. Based on the total mass of the boric acid solution, the mass fraction of B2O3 is 20%, the mass fraction of MoO3 is 0.8%, and the remainder is deionized water. The B2O3 and MoO3 powders are weighed and added to the deionized water and magnetically stirred for 5 hours to obtain the boric acid solution.

[0048] Figure 1-2 The figure shows a schematic diagram of the three-dimensional model of step (2) in Example 1. As can be seen from the figure, the matrix structure is a minimal surface structure.

[0049] The prepared ZTA ceramic green body and the 3D-printed ZTA ceramic-based aluminum borate whisker composite were characterized using scanning electron microscopy, and the results are as follows: Figure 3-4 As shown.

[0050] Figure 3-4 The image shows a scanning electron microscope (SEM) image of the 3D-printed ZTA ceramic-based aluminum borate whisker composite material prepared in Example 1. As can be seen from the image, aluminum borate whiskers are uniformly distributed on the surface of the ZTA ceramic matrix.

[0051] Example 2

[0052] The method for preparing the 3D printed ZTA ceramic-based aluminum borate whisker composite material includes the following steps:

[0053] (1) Dry ZTA powder at 100℃ for 10h, add the dried ZTA powder, photosensitive resin and trisodium citrate into a planetary ball mill, use zirconium oxide grinding balls, the ball-to-material ratio is 4:1, and ball milling is carried out at 200r / min for 12h to obtain printing paste;

[0054] The mass ratio of ZTA powder to photosensitive resin is 80:20; the amount of trisodium citrate added is 5 wt.% of ZTA powder; the viscosity of the printing paste is 800 mPa·s; the photosensitive resin is composed of KH570, tripropylene glycol diacrylate and ethyl 2,4,6-trimethylbenzoylphenylphosphonate in a mass ratio of 80:20:3.

[0055] (2) Construct a three-dimensional model using SolidWorks; import the three-dimensional model into a DLP 3D printer for two-dimensional slicing, and use the printing paste obtained in step (1) to print layer by layer to obtain a ZTA ceramic green body with a preset "pore structure";

[0056] The model parameters are set using parametric controls, specifically: the model length, width, and height are set to 10mm, 10mm, and 6mm respectively; the surface smoothness parameter is set to 10; the pore size adjustment parameter is set to 0.2; the cell type is selected as Gyroid; the period parameter is set to 3.5; the TPMS thickness parameter is set to 0.5; and the wall thickness is set to 2mm. Based on the above parameters, a three-dimensional model with corresponding geometric features and pore structure is generated.

[0057] Set the printing layer thickness to 40μm and the exposure time to 3s;

[0058] (3) The ZTA ceramic green body was placed in a box-type resistance furnace for sintering. The sintering process was as follows: the temperature was raised to 700℃ at a heating rate of 1℃ / min and held for 3h, then raised to 1550℃ at a heating rate of 5℃ / min and held for 4h, and finally cooled to room temperature at a rate of 4℃ / min to obtain the ZTA ceramic matrix.

[0059] (4) The ZTA ceramic matrix was immersed in boric acid solution and ultrasonically soaked for 3 hours at room temperature and 400W. After ultrasonic soaking, it was pre-dried at 70℃ for 1 hour. Then it was placed in a muffle furnace for heat treatment. The heat treatment process was as follows: the temperature was increased to 1000℃ at a rate of 8℃ / min and kept at the temperature in air atmosphere for 4 hours. Finally, the 3D printed ZTA ceramic matrix aluminum borate whisker composite material was obtained.

[0060] The boric acid solution is composed of deionized water, B2O3 and MoO3. Based on the total mass of the boric acid solution, the mass fraction of B2O3 is 25%, the mass fraction of MoO3 is 0.8%, and the remainder is deionized water. The B2O3 and MoO3 powders are weighed and added to the deionized water and magnetically stirred for 6 hours to obtain the boric acid solution.

[0061] Example 3

[0062] The method for preparing the 3D printed ZTA ceramic-based aluminum borate whisker composite material includes the following steps:

[0063] (1) Dry ZTA powder at 100℃ for 10h, add the dried ZTA powder, photosensitive resin and polyacrylic acid into a planetary ball mill, use zirconia grinding balls, the ball-to-material ratio is 4:1, and ball milling is carried out at 200r / min for 12h to obtain printing paste;

[0064] The mass ratio of ZTA powder to photosensitive resin is 90:10; the amount of polyacrylic acid added is 3 wt.% of ZTA powder; the viscosity of the printing paste is 1500 mPa·s; the photosensitive resin is composed of KH570, trimethylolpropane triacrylate and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 70:30:3.

[0065] (2) Construct a three-dimensional model using SolidWorks; import the three-dimensional model into a DLP 3D printer for two-dimensional slicing, and use the printing paste obtained in step (1) to print layer by layer to obtain a ZTA ceramic green body with a preset "pore structure";

[0066] The model parameters are set using parametric controls, specifically: the model length, width, and height are set to 10mm, 10mm, and 6mm respectively; the surface smoothness parameter is set to 10; the pore size adjustment parameter is set to 0.2; the cell type is selected as Gyroid; the period parameter is set to 3.5; the TPMS thickness parameter is set to 0.5; and the wall thickness is set to 2mm. Based on the above parameters, a three-dimensional model with corresponding geometric features and pore structure is generated.

[0067] Set the printing layer thickness to 25μm and the exposure time to 6s;

[0068] (3) The ZTA ceramic green body was placed in a box-type resistance furnace for sintering. The sintering process was as follows: the temperature was raised to 600℃ at a heating rate of 3℃ / min and held for 3h, then raised to 1650℃ at a heating rate of 6℃ / min and held for 3h, and finally cooled to room temperature at a rate of 5℃ / min to obtain the ZTA ceramic matrix.

[0069] (4) The ZTA ceramic matrix was immersed in boric acid solution and ultrasonically soaked for 4 hours at room temperature and 300W. After ultrasonic soaking, it was pre-dried at 70℃ for 1 hour. Then it was placed in a muffle furnace for heat treatment. The heat treatment process was as follows: the temperature was increased to 800℃ at a rate of 5℃ / min and kept at the temperature in air for 6 hours. Finally, the 3D printed ZTA ceramic matrix aluminum borate whisker composite material was obtained.

[0070] The boric acid solution is composed of deionized water, B2O3 and MoO3. Based on the total mass of the boric acid solution, the mass fraction of B2O3 is 15%, the mass fraction of MoO3 is 0.8%, and the remainder is deionized water. The B2O3 and MoO3 powders are weighed and added to the deionized water and magnetically stirred for 5 hours to obtain the boric acid solution.

[0071] Comparative Example 1

[0072] ZTA ceramic matrix prepared in Example 1.

[0073] Comparative Example 2

[0074] The method for preparing the alumina ceramic matrix includes the following steps:

[0075] (1) Dry the alumina powder at 100℃ for 10h, add the dried alumina powder, photosensitive resin and PEG-200 into a planetary ball mill, use zirconia grinding balls, the ball-to-material ratio is 4:1, and ball milling is carried out at 200r / min for 12h to obtain printing paste;

[0076] The mass ratio of alumina powder to photosensitive resin is 88:12; the amount of PEG-200 added is 4 wt.% of alumina powder; the photosensitive resin is composed of KH570, 1,6-hexanediol diacrylate and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of 75:25:3.

[0077] (2) Construct a three-dimensional model using SolidWorks; import the three-dimensional model into a DLP 3D printer for two-dimensional slicing, and use the printing paste obtained in step (1) to print layer by layer to obtain alumina ceramic green body with a preset "pore structure";

[0078] The model parameters are set using parametric controls, specifically: the model length, width, and height are set to 10mm, 10mm, and 6mm respectively; the surface smoothness parameter is set to 10; the pore size adjustment parameter is set to 0.2; the cell type is selected as Gyroid; the period parameter is set to 3.5; the TPMS thickness parameter is set to 0.5; and the wall thickness is set to 2mm. Based on the above parameters, a three-dimensional model with corresponding geometric features and pore structure is generated.

[0079] Set the printing layer thickness to 30μm and the exposure time to 5s;

[0080] (3) The alumina ceramic green body is placed in a box-type resistance furnace for sintering. The sintering process is as follows: the temperature is raised to 800℃ at a heating rate of 2℃ / min and held for 2h. Then the temperature is raised to 1600℃ at a heating rate of 4℃ / min and held for 2h. Finally, the temperature is lowered to room temperature at a rate of 3℃ / min to obtain the alumina ceramic matrix.

[0081] The flexural strength and fracture toughness of the ceramic matrices prepared in the examples and comparative examples were tested respectively, and the test methods are as follows:

[0082] Bending strength (MPa) was tested in accordance with GB / T 6569-2006;

[0083] Fracture toughness (MPa·m) 1 / 2 Tests were conducted in accordance with GB / T 23806-2009;

[0084] The water contact angle and oil contact angle of the 3D printed ZTA ceramic-based aluminum borate whisker composite material prepared in the examples and the ceramic matrix of the comparative examples were tested respectively. The test methods are as follows:

[0085] Water contact angle (°) shall be tested in accordance with GB / T 30693-2014;

[0086] Oil contact angle (°) shall be tested in accordance with GB / T 30693-2014;

[0087] Oil-water separation tests were conducted on the 3D-printed ZTA ceramic-based aluminum borate whisker composite material prepared in the examples and the ceramic matrix of the comparative example. An oil-water mixture with an oil content of 30 wt.% was prepared by mixing 3 g of oil and 7 g of water. The composite material prepared in the examples and the ceramic matrix of the comparative example were respectively loaded into a sand core filter device assembled from a measuring cylinder, a sand core filter head, and a suction flask. The solid structure at the edge of the composite material or ceramic matrix was compacted and sealed with a rubber sealing ring to ensure that the oil-water mixture flowed only through the material channels. The oil-water mixture was separated by passing it through the sand core filter device, with the processing flow rate controlled at 150 L / (m²). 2 •h), operating pressure 0.2MPa, temperature 25℃.

[0088] The separation efficiency (%) is calculated using the formula: ((initial mass of oil - mass of oil collected permeating through the sand core filter) / initial mass of oil) × 100%.

[0089] The formula is: Outflow volume (L) / (Effective filtration area (m²)) 2 The permeation flux (L / (m³)) is calculated by multiplying the filtration time (h) by the permeation flux. 2 ·h)).

[0090] The test results are shown in Table 1.

[0091] Table 1 Performance Test Results

[0092]

[0093] As can be seen from Table 1, the composite materials prepared in Examples 1-3 have low water contact angles and high oil contact angles, exhibiting excellent "hydrophilic-oleophobic" properties. The corresponding separation efficiency and permeation flux are much higher than those of Comparative Examples 1-2, and the performance degradation is small after 50 cycles. This indicates that the composite material of the present invention has significant advantages in terms of high efficiency and stability in oil-water separation.

[0094] The ZTA ceramic matrix obtained exhibits good overall flexural strength and fracture toughness. The fracture toughness of the alumina ceramic matrix in Comparative Example 2 is much lower than that of the ZTA ceramic matrix, indicating that the mechanical reliability of the ceramic matrix is ​​not significantly affected while ensuring separation performance. In contrast, the mechanical property defects of Comparative Example 2 would limit its pressure resistance and damage resistance in practical applications.

[0095] In summary, the composite material of this invention is superior to the comparative group in both oil-water separation performance and mechanical properties, achieving synergistic optimization of "high-efficiency separation - stable circulation - mechanical reliability".

Claims

1. A method for preparing a 3D printed ZTA ceramic based aluminum borate whisker composite material, characterized in that, The method comprises the following steps: (1) mixing ZTA powder, photosensitive resin and dispersant by ball milling to obtain printing slurry; (2) constructing a three-dimensional model by using SolidWorks; importing the three-dimensional model into a DLP 3D printer for two-dimensional slicing processing; using the printing slurry prepared in step (1) to print a ZTA ceramic green body layer by layer; (3) sintering the ZTA ceramic green body to obtain a ZTA ceramic matrix; (4) immersing the ZTA ceramic matrix in a boric acid solution, and then performing ultrasonic immersion, drying and heat treatment to obtain a 3D printed ZTA ceramic matrix aluminum borate whisker composite material; The ZTA powder is a composite powder of 3mol% yttria-stabilized zirconia and aluminum oxide; wherein the zirconia accounts for 10-20wt.% of the total amount of the ZTA powder; the particle size of the ZTA powder is 0.5-2μm; The mass ratio of the ZTA powder to the photosensitive resin is 80-90:10-20; the addition amount of the dispersant is 1-5wt.% of the ZTA powder; and the viscosity of the printing slurry is 500-1500mPa·s; The photosensitive resin is composed of KH570, active diluent and photoinitiator with a mass ratio of 70-80:20-30:3; the active diluent is one or more of 1,6-hexanediol diacrylate, 1,4-hexanediol diacrylate, tripropyleneglycol diacrylate, hydroxyethyl acrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate or pentaerythritol acrylate; and the photoinitiator is one or more of 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide or 2-phenyl benzyl-2-dimethylamine-1-(4-morpholinobenzyl) butanone; In step (4), the boric acid solution is composed of deionized water, B2O3 and MoO3; based on the total mass of the boric acid solution, the mass fraction of B2O3 is 15-25%, the mass fraction of MoO3 is 0.5-1%, and the balance is deionized water; and the heat treatment process is as follows: heating at a rate of 5-8℃ / min to 800-1000℃, and then holding in an air atmosphere for 2-6h.

2. The method of claim 1, wherein the 3D printed ZTA ceramic aluminum borate whisker composite material is characterized by: The dispersant is one of PEG-200, trisodium citrate or polyacrylic acid.

3. The method of claim 1, wherein the 3D printed ZTA ceramic matrix aluminum borate whisker composite is characterized by: In step (2), the printing layer thickness is 25-40μm, and the exposure time is 3-6s.

4. The method of claim 1, wherein the 3D printed ZTA ceramic-based aluminum borate whisker composite material is characterized by: In step (3), the sintering process is as follows: heating at a rate of 1-3℃ / min to 600-800℃, holding for 2-3h, then heating at a rate of 4-6℃ / min to 1550-1650℃, holding for 2-4h, and finally cooling to room temperature at a rate of 3-5℃ / min.

5. A 3D printed ZTA ceramic based aluminum borate whisker composite material, characterized in that, The 3D printed ZTA ceramic matrix aluminum borate whisker composite material is prepared by using the preparation method of any one of claims 1-4.

6. Use of the 3D printed ZTA ceramic based aluminum borate whisker composite material of claim 5, characterized in that, The 3D printed ZTA ceramic matrix aluminum borate whisker composite material is used for oil-water separation of oil-containing wastewater.

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